2-cyano-4-nitro-6-halogeno-2&#39;-acylamino-4&#39;-dialkylamino-1, 1&#39;-azobenzene dyes



United States Patent ()ffice 3,398,135 Patented Aug. 20, 1968 3,398,1352CYANO4NITRO-6-HALOGENO-2'-ACYLAMINO- 4'-DIALKYLAMlN0-1,1-AZOBENZENEDYES Curt Mueller, Basel, Basel-Stadt, Switzerland, assignor to SandozLtd. (also known as Sandoz AG), Basel,

Switzerland No Drawing. Continuation-impart of application Ser. No.344,538, Feb. 13, 1964. This application June 21, 1967, Ser. No. 647,641

Claims priority, application S/vgitzerland, Feb. 15, 1963,

3 Q 10 Claims. (Cl. 260205) ABSTRACT OF THE DISCLOSURE Disperse dyes ofthe 2-cyano-4-nitro-6-halogeno-2'-acylamino-4'-dialkylamino-1,1'-azobenzene series build up excellentlyfrom aqueous dispersion on textile materials made of fully synthetic orsemi-synthetic hydrophobic high molecular organic substances. Resultingdyeings are extremely fast to thermofixation, sublimation, pleating, gasfumes, cross-dyeing, dry cleaning, chlorine, water, washing andperspiration.

This application is a continuation-in-part of application Ser. No.344,538 filed Feb. 13, 1964, and now US. Patent No. 3,342,804.

This invention relates to dyes of the formula wherein A represents achlorine or bromine atom, B represents an alkyl radical having 1 or 2carbon atoms, which may be substituted by a chlorine or bromine atom ora cyano, phenyloxy or low molecular alkoxy radical, D represents a lowmolecular alkyl radical, E represents a low molecular alkyl radical andY represents 3. COO or SO radical.

The term low molecular designates radicals having 1, 2, 3 or 4 carbonatoms.

These dyes are produced by coupling a diazotized In general the couplingreaction is conducted in an acid, if necessary buffered medium, withcooling, for example at temperatures between and 5 C.

Applied from aqueous dispersion, these dyes build up excellently ontextile materials made of fully synthetic or semi-synthetic hydrophobichigh-molecular substances. They are especially suitable for the dyeing,padding and printing of filaments, fibers, fleeces, knitted fabrics andwoven fabrics made of linear aromatic polyesters, secondary celluloseacetate, or cellulose triacetate; synthetic polyamides, polyolefinsandacrylonitrile polymerisation products can also be dyed with the dyes.Dyeings of high quality are obtained on linear aromatic polyesters.These are generally polycondensation products of terephthalic acid andglycols, notably ethylene glycol.

It is of great advantage to convert the dyes into dyeing preparations byone of the known methods before they are applied to the textilematerial. For this purpose they are ground to an average particle sizeof approximately 0.01 to 10 microns or preferably about 0.1 to 5microns. Grinding can be carried out in the presence of dispersingagents or filling agents. For example, the dried dye can be ground witha dispersing agent, if necessary in the presence of filling agents oritcan be kneaded in paste form with a dispersing agent and dried in avacuum or jet drier. The preparations obtained in this Way, on theaddition of a suitable volume of water, are useful for dyeing fromso-called long baths, for padding or for printing.

For dyeing in long baths amounts of dye up to about 100 grams per literare generally used, for padding up to about 150 grams per liter, orpreferably 0.1 to 100 grams and for printing up to about 150 grams perkilogram of printing paste. The liquor ratio can vary within widelimits, e.g. from about 1:3 to 1:200 or preferably between 1:3 and 1:80.

The known dyeing methods are used for the dyes. Polyester fibers can bedyed in the presence of carriers at temperatures from about to 125 C. orin the absence of carriers at about to 140 C. under pressure by theexhaustion process. The dyes can be padded on these fibers from aqueusdispersion or printed with an aqueous paste, and fixed at temperaturesbetween 140 C. and 230 C., e.g. with the aid of water vapour or air. Inthe optimum temperature range 180 to 220 C. the dyes diffuse rapidlyinto the polyester fiber and do not sublime even when the fiber isexposed to these high temperatures for some length of time. Thiseliminates the inconvenience caused by contamination of the fixing plantby sublimed dye. Secondary cellulose acetate is dyed preferably attemperatures between about 65 and 80 C. and cellulose triacetate attemperatures up to about C. The optimum pH range is 2 to 9 or moreparticularly 4 to 8.

In most cases one of the dispersing agents in general use is added tothe dye-bath; these are preferably anionic or non-ionic and may beemployed in mixture with each other. Approximately 0.5 gram dispersingagent per liter of the dyeing medium is often sufficient, but largeramounts, eg to about 3 grams per liter, can 'be used.

The dyeings and prints obtained are extremely fast to thermofixation,sublimation, pleating, gas fumes, cross dyeing, dry cleaning, chlorine,and to wet treatments, e g. water, washing and perspiration. They arewell dischargeable and the reserve of cotton and wool is good. The lightfastness is outstanding even in pale shades, which makes the new dyeshighly suitable as components for combination dyeings in fashionablepastel shades. The dyes are stable to boiling and reduction attemperatures up to 220 C. and in particular within the range 80 C. to140 C. This stability is not adversely atfected either by the liquorratio or by the presence of agents accelerating the dyeing process.

In the following examples the parts are by weight and the temperaturesin degrees centigrade.

Example 1 6.9 parts of sodium nitrite are added slowly with stirring toparts of concentrated sulphuric acid at 60- 70 After stirring foranother 10 minutes at 60 the solution is cooled to 10 and 100 parts ofglacial acetic acid followed by 19.7 parts of2-amino-3-chloro-5-nitrobenzonitrile and 100 parts of glacial aceticacid are added at 1020. Stirring is continued for 2 hours, then 10 partsof urea are added to the diazonium salt solution and after 10 minutes itis run into a cold mixture of 23.6 parts of3-diethylamino-1carbethoxyaminobenzene, 20 parts of concentratedhydrochloric .acid and 100 parts of ice. The coupling reaction isbrought to a close in acid medium at The dye formed is filtered off,washed free of acid and dried. It dyes synthetic fibers in violet shadeswith good wherein A is a member selected from the group consisting ofchloro and bromo; B is a member selected from the group consisting offastness properties. unsubstituted alkyl having from 1 to 2 carbon atomsExample 2 and substituted alkyl wherein the alkyl has from 1 i to 2carbon atoms and any substituent is selected 69 parts of powderedSOdllllTl nitrite are added slowly f 'th group on i ti of chloro,brorno, cyano, with vigorous stirring to 150 parts of concentrated sulhn l d l r alkoxy; furic acid at 60-70". After stirring for a further 10p D isl wer lk l; minutes at 60 and cooling to 0, 19.7 parts of Z-amino-E i l wer alkyl; and 3-chloro-S-nitrobenzonitrile are added at thistempera- Y is a member selected from the group consisting of ture.Stirring is continued for 2 hours and the resulting CO0 d 50 a diazoniumsalt solution is run into a cold mixture of z, A d according t l i 1 h iB i b i- 24.2 parts of 3-diethyla1nino 1 methylsulfonylamino- {m d lk l,n Parts Of Concentrated lfydfochlofic f 150 3. A dye according to claim1 wherein B is chloroalkyl. parts of Ice and 10 parts of ammosulfomcacid. The 4, A dye. according to claim 1 wherein B is bromocouplingreaction is brought to a close in acid medium at lk l, 0 which may bebuttered. The dye formed iS filtered Off, 5, A dye according to claim 1wherein B is phenyloxy- Washed free of acid and dried. On syntheticfibers it yields alkyl brilliant violet shades with good fastnessproperties. 6, A dye a ording to claim 1 wherein B is lower Thedyestuffs listed in the following table are produced alkoxyalkyl. in thesame manner as given in the preceding examples. 7. A dye according toclaim 1 wherein B is cyanoalkyl.

TABLE I Example Shade on No. A B D E Y Polyester Fibers CH2CH2C1 -C2H5C2H5 OOO Blue. CH CH3 -CH3 -0oo Do. -C H -CH OH 0o0 D0. CzH4Br C2H CzH5OOO Do. 'C2H5 -C2H5 OzH5 -COO- Ggelenish 432115 412115 O2H -coo b d.-02Hi01 -C2H G H --CO O Blue. OHa 2 s -C9H5 -SO2- Do. --CH3 -CH3 CI13-SO2-' D0. --CH;; -C2Hs C2H5 -SO2 D0. C2H5 C3H1 -C3H7 -COO-- D0. --CH2CN-C9H5 --C2H5 -COO- D0. GH2OCH3 .C2H5 O2H5 GOO- D0. -CH2OC2H5 -C3H7 -C3H7-SO2- D0. --CH OC Hs --C2H5 -C2H5 O0O D0. -CHC1CH -CzH OzH COO Do. CH3C4Hg C4Hg SO2 D0. 0H2-0-c;11 -C2Hi -C2H5 COO D0. CH2CN C2H5 C2H5 SO2 DO.

Formulae of representative dyes of the foregoing eX- 8. The dyeaccording to claim 1 of the formula amples are as follows: GN

CzH5 Example 2 OgN N=N N 0 H ON 02135 1 NH-SOa-OH; 2 5 C Q 9. The dyeaccording to claim 1 of the formula ON 01 NH 0 on /C2H5 -s za o N -N=N NExample 12 \CQHS Br NHSO2OH2 CN v I /O2Hs 10. The dye acgcgdmg to claim1 of the formula omQ- N\ /C2H5 B- NH 0 CH CZHE O2N 1 S za {a 02115 1'Example 3 NHCOOGH2CH2C1 ON C H References Cited 0 O a 5 UNITED STATESPATENTS r 2,155,755 4/1939 Felix et a1 260-207 cam 60 2,286,795 6/1942Dickey et al 260207.1 NHCOO--CH2CH2C1 3,178,405 4/1965 Merian 260-207 Hm d l d h h t 1 3,268,507 8/1966 Kruckenberg 260207.1 XR

aving us rsc ose t e invention w a we c alm 1s: 1. A dye of the formulaFOREIGN PATENTS 852,493 10/ 1960 Great Britain. CN 856,348 12/1960 GreatBritain. f 865,328 4/1961 Great Britain. om-QMNQI 1,365,849 5/1964France.

A E FLOYD D. HIGEL, Primary Examiner.

